EP0902754B1 - Method for inducing hydrogen desorption from a metal hydride - Google Patents

Method for inducing hydrogen desorption from a metal hydride Download PDF

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Publication number
EP0902754B1
EP0902754B1 EP97920469A EP97920469A EP0902754B1 EP 0902754 B1 EP0902754 B1 EP 0902754B1 EP 97920469 A EP97920469 A EP 97920469A EP 97920469 A EP97920469 A EP 97920469A EP 0902754 B1 EP0902754 B1 EP 0902754B1
Authority
EP
European Patent Office
Prior art keywords
desorption
metal hydride
hydrogen
energy
hydride
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP97920469A
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German (de)
English (en)
French (fr)
Other versions
EP0902754A1 (en
Inventor
Alicja Zaluska
Leszek Zaluski
John Strom-Olsen
Robert Schulz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hydro Quebec
Original Assignee
McGill University
Hydro Quebec
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Filing date
Publication date
Application filed by McGill University, Hydro Quebec filed Critical McGill University
Priority to EP03014112A priority Critical patent/EP1382566A1/en
Publication of EP0902754A1 publication Critical patent/EP0902754A1/en
Application granted granted Critical
Publication of EP0902754B1 publication Critical patent/EP0902754B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
    • C01B6/04—Hydrides of alkali metals, alkaline earth metals, beryllium or magnesium; Addition complexes thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
    • C01B6/24—Hydrides containing at least two metals; Addition complexes thereof
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C11/00—Use of gas-solvents or gas-sorbents in vessels
    • F17C11/005—Use of gas-solvents or gas-sorbents in vessels for hydrogen
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/32—Hydrogen storage
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the present invention relates to a method for inducing desorption of hydrogen from a metal hydride containing the same, in which a non-thermal energy source is used to induce such desorption.
  • Metal hydrides are potentially ideal candidates for hydrogen storage and transportation. As hydrogen carriers, they provide high hydrogen storage capacities (up to for example 7.6 wt. % in Mg 2 H 2 ) and full safety. The safety is provided by endothermic reaction of hydrogen release, which excludes spontaneous (explosive) or uncontrolled reaction.
  • Metal hydrides are advantageous in that they can be handled and stored at ambient temperature without any atmosphere or pressure requirements. Such makes them economically favorable by elimination of cryogenic equipment necessary to use with liquid hydrogen or activated charcoal.
  • GB-A-1568374 and GB-A-2 164 637 disclose metallic hydride hydrogen storages and respectively process for the supply of hydrogen from a metallic hydride material.
  • Metal hydrides are also very stable. Such is advantageous from a safety and economical point of view. However, because of their stability, most of the metal hydrides require elevated temperatures to initiate desorption.
  • metal hydrides having a high stability are MgH 2 or Mg 2 NiH 4 . They exhibit excellent hydrogen storage potential - with large hydrogen storage capacity (7.65 wt. % for MgH 2 or 3.6 wt. % for Mg 2 NiH 4 ), low cost of the material and easy handling. However, desorption of hydrogen from these hydrides with reasonable kinetics requires heating to high temperatures: 350 - 400°C for MgH 2 and 330 - 360°C for Mg 2 NiH 4 .
  • the object of the present invention is to provide an alternative approach to facilitate desorption of hydrogen from a high temperature metal hydride.
  • the invention is based on the discovery that, instead of using a conventional heat source, use can be made of a non-thermal energy source to initiate hydrogen release and thus to induce hydrogen desorption.
  • non-thermal energy sources does not necessary exclude energy sources where heat is produced, like electric energy where heat is produced by Joule effect.
  • this expression is exclusively used to exclude “conventional” heat sources such as gas or oil burners where heat is produced and transferred mainly by convection to the metal hydrides.
  • the present invention as broadly claimed hereinafter, is directed to a method for inducing desorption of hydrogen from a metal hydride by applying thereto sufficient energy to induce hydrogen desorption by endothermic reaction, wherein the energy that is so applied is non-thermal and consists of mechanical energy.
  • the invention is based on the discovery that instead of using a heat source as it has been done so far, use can be made of a non-thermal energy source to induce hydrogen desorption from a metal hydride.
  • This energy is applied directly on the metal hydride.
  • One way to apply the energy directly to the metal hydride consists in introducing an accumulating energy in the hydride to cause desorption by mechanical energy (in the form of strain and defects).
  • desorption is much easier than when the hydride is activated by heat. Moreover, after mechanical pretreatment, the desorption temperature is significantly reduced.
  • the method of inducing hydrogen desorption from a metal hydride consists of applying mechanical energy by ball milling to a powder of the metal hydride (which is the usual form of metal hydride). It is well established that ball milling is capable of generating a sufficient amount of mechanical energy to cause formation of various compounds (nitrides, borides,) or alloys (mechanical alloying). In the present case, ball milling can be used either to decompose the metal hydride and release hydrogen, or to accumulate so much strain and defects in the hydride that further heat-activated desorption is facilitated. Temperature of desorption of metal hydrides treated mechanically may be then reduced by 100 - 200°C, which is of great significance for practical application.
  • the method according to the invention may be used for inducing hydrogen desorption in disposable hydrogen storage tanks (for camping units or similar use).
  • Fig. 1 are differential scanning calorimetry (DSC) curves of a Mg-based hydride as prepared (a) and after 2, 7 and 9 minutes of ball milling (curves (b), (c) and (d), respectively).
  • DSC differential scanning calorimetry
  • a Mg-based hydride was submitted to a mechanical pretreatment before desorption.
  • it In the as-prepared state, it exhibited a high temperature of desorption equal to about 400°C, when measured by differential scanning calorimetry (DSC) at continuous heating with heating rate of 40 K/min (see Fig. 2, curve a).
  • DSC differential scanning calorimetry
  • Ball milling in a SPEX® mill caused a decrease in the desorption temperature due to an accumulation of mechanical energy in the form of strain and defects.
  • Curves b, c and d represent effects of ball milling of the hydride for 2, 7, 9 min., respectively.
  • the temperature of desorption was decreased by 200°C in the last case (see Fig. 2).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Filling Or Discharging Of Gas Storage Vessels (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
EP97920469A 1996-05-13 1997-05-13 Method for inducing hydrogen desorption from a metal hydride Expired - Lifetime EP0902754B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP03014112A EP1382566A1 (en) 1996-05-13 1997-05-13 Method for inducing hydrogen desorption from a metal hydride

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US08/645,352 US5882623A (en) 1996-05-13 1996-05-13 Method for inducing hydrogen desorption from a metal hydride
US645352 1996-05-13
PCT/CA1997/000324 WO1997043206A1 (en) 1996-05-13 1997-05-13 Method for inducing hydrogen desorption from a metal hydride

Publications (2)

Publication Number Publication Date
EP0902754A1 EP0902754A1 (en) 1999-03-24
EP0902754B1 true EP0902754B1 (en) 2003-08-06

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Application Number Title Priority Date Filing Date
EP97920469A Expired - Lifetime EP0902754B1 (en) 1996-05-13 1997-05-13 Method for inducing hydrogen desorption from a metal hydride
EP03014112A Withdrawn EP1382566A1 (en) 1996-05-13 1997-05-13 Method for inducing hydrogen desorption from a metal hydride

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP03014112A Withdrawn EP1382566A1 (en) 1996-05-13 1997-05-13 Method for inducing hydrogen desorption from a metal hydride

Country Status (7)

Country Link
US (2) US5882623A (enrdf_load_stackoverflow)
EP (2) EP0902754B1 (enrdf_load_stackoverflow)
JP (1) JP2000515107A (enrdf_load_stackoverflow)
CN (1) CN1094895C (enrdf_load_stackoverflow)
CA (1) CA2254858C (enrdf_load_stackoverflow)
DE (1) DE69723977T2 (enrdf_load_stackoverflow)
WO (1) WO1997043206A1 (enrdf_load_stackoverflow)

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US7157401B2 (en) * 2002-10-17 2007-01-02 Carnegie Mellon University Catalyst for the treatment of organic compounds
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WO2004094306A1 (ja) * 2003-04-21 2004-11-04 Techno Network Shikoku Co. Ltd. 水素発生装置および水素発生方法
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JP2007512213A (ja) * 2003-09-30 2007-05-17 ゼネラル・エレクトリック・カンパニイ 水素吸蔵組成物及びその製造方法
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Also Published As

Publication number Publication date
US5882623A (en) 1999-03-16
CN1222894A (zh) 1999-07-14
EP1382566A1 (en) 2004-01-21
CA2254858A1 (en) 1997-11-20
DE69723977D1 (de) 2003-09-11
CN1094895C (zh) 2002-11-27
WO1997043206A1 (en) 1997-11-20
JP2000515107A (ja) 2000-11-14
CA2254858C (en) 2002-07-30
EP0902754A1 (en) 1999-03-24
US6080381A (en) 2000-06-27
DE69723977T2 (de) 2004-07-29

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